Controlled subnanosecond isomerization of HCN to CNH in solution

Journal Article · Sun May 22 00:00:00 EDT 2005 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.1913398· OSTI ID:20722251

Jiangbin, Gong; Ao, Ma; Rice, Stuart A ^[1]

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1. Department of Chemistry and James Franck Institute, University of Chicago, Chicago, Illinois 60637 (United States)

We report a study of control of the HCN{yields}CNH isomerization in a liquid Ar solution. We show, using molecular dynamics simulations, nearly complete conversion from HCN to CNH can be achieved in solution on the subnanosecond time scale without requiring laser pulse shaping or molecular alignment. The mechanism of the isomerization reaction involves multiphoton rovibrational excitation on the ground electronic state potential energy surface coupled with rapid rovibrational relaxation in solution. The results demonstrate the important role of rotation-vibration coupling in multiphoton excitation of small molecules and constitute the first realistic computational demonstration of fast, robust, and high-yield laser field manipulation of solution-phase molecular processes.

• OSTI ID: 20722251
• Journal Information: Journal of Chemical Physics, Vol. 122, Issue 20; Other Information: DOI: 10.1063/1.1913398; (c) 2005 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ENERGY TRANSFER
EXCITATION
GROUND STATES
HYDROCYANIC ACID
ISOMERIZATION
LASER RADIATION
MOLECULAR DYNAMICS METHOD
MULTI-PHOTON PROCESSES
PHOTOCHEMISTRY
PHOTON-MOLECULE COLLISIONS
REACTION KINETICS
ROTATIONAL STATES
SIMULATION
SOLUTIONS
VIBRATIONAL STATES